Aqueous glittering ink composition

ABSTRACT

The glittering ink composition of the present invention contains a glass flake pigment, a water-soluble resin, a water-soluble organic solvent and water as essential ingredients. The content of the glass flake pigment is 0.01-40% by weight relative to the total amount of the ink composition. Moreover, the ink composition contains a synthetic resin emulsion as a binder component for fixing the glass flake pigment to a handwriting or a coated film in 0.01-40% by weight in solids relative to the total amount of the ink composition. The synthetic resin emulsion has an anionic property or a nonionic property and its minimum film forming temperature is not higher than 20° C.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. patent applicationSer. No. 09/523,619, filed Mar. 13, 2000, said application being herebyincorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an aqueous glittering ink compositionwhich can be suitably used for writing tools, printing inks, fieldspertaining to coatings, cosmetics, and the like.

2. Description of the Prior Art

Heretofore, for the purpose of obtaining a handwriting with metallicluster such as gold and silver, aqueous ink compositions usingglittering pigments have been proposed. For example, Japanese UnexaminedPatent Publication No. 7-118592 proposes an aqueous ink compositionusing an aluminum powder pigment. Japanese Unexamined Patent PublicationNo. 8-151547 proposes an ink composition using a pearlescent pigment.Japanese Unexamined Patent Publication No. 11-29734 proposes an aqueousmetallic ink prepared by coloring an aluminum powder with an organicpigment using a fixing agent.

However, in the case of such conventional aqueous ink compositions usingglittering pigments such as aluminum powder pigment, pearlescent pigmentand the like, it has been difficult to obtain handwritings or coatingfilms with strong glittering feeling and spatial effect. Moreover,although in order to obtain metallic color a method has been adopted inwhich these glittering pigments are colored with coloring materials suchas dyes and pigments, there has been a problem that the glitteringfeeling is lost in the coloring step because of the use of a resin.

The object of the present invention is to provide aqueous glittering inkcompositions which can provide handwritings or coating films having astronger glittering feeling in comparison with aqueous ink compositionsusing conventional glittering pigments, and moreover having together astrong spatial effect which conventional ink compositions never have.

The other object of the present invention is to provide aqueousglittering ink compositions which can provide handwritings or coatedfilms having a strong glittering feeling without losing glitter incomparison with aqueous ink compositions using conventional glitteringpigments.

SUMMARY OF THE INVENTION

As a result of intensive studies for achieving the aforementionedobjects, the present inventors have adopted an aqueous glittering inkcomposition containing, at least, a glass flake pigment, a water-solubleresin, a water-soluble organic solvent and water. Furthermore, thepresent inventors have adopted an aqueous glittering ink compositioncontaining, at least, a metal coated inorganic pigment, a water-solubleresin, a water-soluble organic solvent and water. The “metal coatedinorganic pigment” used in the present invention is defined as a generalterm for inorganic pigments coated with at least one substance of metaland metal oxide.

Accordingly, the aqueous glittering ink composition containing the glassflake pigment can provide a handwriting or a coated films having astronger glittering feeling and spatial effect than these achieved byaqueous ink compositions using conventional glittering pigments such asan aluminum powder pigment and a pearlescent pigment, because of thehigh surface smoothness inherent to glass.

Moreover, the aqueous glittering ink composition containing the metalcoated inorganic pigment also can provide a handwriting or a coated filmhaving a stronger glittering feeling than that achieved by aqueous inkcompositions using conventional glittering pigments without losingglitter, because the inorganic pigment has been colored with metaldeposition or the like.

DESCRIPTION OF THE PREFERRED EMBODIMENT

(Glass Flake Pigment)

The glass flake pigment used in the present invention is defined as apigment which has a structure wherein a flaky glass is coated with metalor the like and has a glittering feeling and spatial effect. As anexample, a glass flake pigment formed of a flaky glass coated with metalby electroless plating can be used. For example, ones coated with silveravailable from Toyo Aluminium Co., Ltd. under the trade names of“Metashine REFSX-2015PS”, “Metashine REFSX-2025PS” and “REFSX-2040PS”can be mentioned.

In addition, a glass flake pigment formed of a flaky glass coated withmetal by spattering can also be used. For example, ones coated withsilver available from Toyo Aluminium Co., Ltd. under the trade names of“Crystal Color GF2125”, “Crystal Color GF2125-M”, “Crystal Color GF2140”and “Crystal Color GF2140-M” can be mentioned. Also ones coated withnickel-chromium-molybdenum available from the same company under thetrade names of “Crystal Color GF2525”, “Crystal Color GF2525-M”,“Crystal Color GF2540” and “Crystal Color GF2540-M” can be mentioned.Also, one coated with brass available from the same company under thetrade name of “Crystal Color GF250”, one coated with silver alloyavailable from the same company under the trade name of “Crystal ColorGF1345”, and one coated with titanium available from the same companyunder the trade name of “Crystal Color GF1445” can be mentioned.

In the present invention, the glass flake pigment preferably has amedian diameter of 5.0-100 μm. When the median diameter of the glassflake pigment is less than 5.0 μm, the flake particles are so small thatthe glittering feeling becomes poor. On the other hand, the mediandiameter of the glass flake pigment of greater than 100 μm isunfavorable because the ink does not come out of a pen tip easily.

The glass flake pigment of the present invention is preferably containedin 0.01-40% by weight relative to the total amount of the inkcomposition. When the content of the glass flake pigment is less than0.01% by weight relative to the total amount of the ink composition,only unsatisfactory glittering feeling and spatial effect can beobtained. When the content of the glass flake pigment exceeds 40% byweight relative to the total amount of the ink composition, theviscosity of the ink increases so high that the fluidity and writingperformance of the ink become poor. The optimum content of the glassflake pigment ranges 0.5-30% by weight.

(Metal Coated Inorganic Pigment)

The metal coated inorganic pigment to be used in the present inventioncomprises, for example, an inorganic pigment which is coated with metalor metal oxide by means of metal deposition or the like. For example,aluminum coated with iron(III) oxide can be used. For example, onesavailable from BASF AG under the trade names of “Paliocrom Gold L2000”,“Paliocrom Gold L2002”, “Paliocrom Gold L2020”, “Paliocrom Gold L2022”,“Paliocrom Gold L2025”, and “Paliocrom Orange L2800” can be mentioned.In addition, mica coated with iron(III) oxide can also be used. Forexample, ones available from BASF AG under the trade names of “PaliocromRed Gold L2500” and “Paliocrom Red L4000” can be mentioned. Moreover,mica-like iron(III) oxide coated with aluminum-manganese can be used.For example, ones available from BASF AG under the trade names of“Paliocrom Copper L3000” and “Paliocrom Copper L3001” can be mentioned.Mica coated with reduced titanium dioxide can also be used. Forinstance, ones available from BASF AG under the trade names of“Paliocrom Blue Silver L6000” and “Paliocrom Blue Silver L6001” can bementioned. Moreover, mica coated with titanium dioxide can also be used.

A median diameter of the aforementioned metal coated inorganic pigmentalso preferably ranges from 5.0-100 μm in common with the glass flakepigment. The case in which the median diameter is less than 5.0 μm isunfavorable because the inorganic pigment particle is so small that theglittering feeling becomes poor. The case in which the median diameterexceeds 100 μm is also unfavorable because when the metal coatedinorganic pigment is used in the form of ink for ball-point pens, itdoes not come out of the pen tip easily.

As for the amount of the metal coated inorganic pigment to becompounded, the pigment is preferably contained in 0.01-40% by weightrelative to the total amount of the ink composition in common with theglass flake pigment. When the content of the inorganic pigment is lessthan 0.01% by weight relative to the total amount of the inkcomposition, the glittering feeling becomes unsatisfactory. When theinorganic pigment exceeds 40% by weight relative to the total amount ofthe ink composition, the viscosity of the ink becomes so high that thefluidity is reduced. The optimum content of the inorganic pigment rangesfrom 0.5-30% by weight.

(Water-soluble Organic Solvent)

Water-soluble organic solvents capable of preventing both drying at thepen tip and freezing of the ink are preferably used, which can beexemplified by glycols such as ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol and polyethylene glycol, polyhydricalcohols such as glycerin, glycol ethers such as ethylene glycolmonomethyl ether, diethylene glycol monomethyl ether, dipropylene glycolmonomethyl ether and dipropylene glycol monopropyl ether. These organicsolvents may be used alone or in combinations of two or more of them.

The content of the water-soluble organic solvent is preferably containedin 1.00-40% by weight relative to the total amount of the inkcomposition. When the content of the water-soluble organic solvent isless than 1.00% by weight relative to the total amount of the inkcomposition, the pen tip becomes susceptible to dry and the ink becomesliable to freeze. When the content of the water-soluble solvent exceeds40% by weight relative to the total amount of the ink composition, ahandwriting or a coated film is difficult to dry out as well assolubility of the water-soluble resin being influenced. The optimumcontent of the water-soluble organic solvent, which varies depending onits type, ranges from 5.00-20% by weight.

(Colorant)

A colorant can be used in the present invention. The use of a colorantcan adjust the ink colors to a variety of colors. It is important thatsuch a colorant should be used as does not react with the aforementionedglass flake pigment or metal coated inorganic pigment nor does itinfluence coloring of such a glass flake pigment or metal coatedinorganic pigment. Moreover, colorants with high solubility anddispersibility are favorable.

Examples include water-soluble dyes such as acid dyes, direct dyes andbasic dyes, inorganic pigments such as carbon black and titanium oxide,organic pigments such as copper phthalocyanine pigments, threnepigments, azo pigments, quinacridon pigments, anthraquinone pigments,dioxane pigments, indigo pigments, thioindigo pigments, perinonepigments, perylene pigments, indolenone pigments and azomethinepigments, and fluorescent pigments, colored resin emulsions and the likecan be mentioned. These also may be used in the form of a pigmentdispersion. The present invention can use one species of pigment or canuse two or more species of pigments in combination. Moreover, the glassflake pigment or metal coated inorganic pigment in the present inventioncan be used after being mixed with glittering pigments includingaluminum powder pigments and pearlescent pigments. Furthermore, they canbe mixed with opacifying pigments including a variety of inorganic ororganic white pigments such as titanium oxide, alkylene bismelaminederivatives, plastic pigments (synthetic resin particle pigments) withopacifying power of various shapes including spherical shapes, oblateshapes and the like. The metal coated inorganic pigment also can be usedtogether with the glass flake pigment.

Such a colorant need not be contained in the aqueous ink composition ofthe present invention. Even aqueous ink compositions containing notcolorants but glass flake pigments or metal coated inorganic pigmentscan provide high glittering feeling and high spatial effect tohandwritings or coated films. Also even aqueous ink compositions notcontaining colorants but containing metal coated inorganic pigments canadd high glittering feeling to handwritings or coated films. Theaforementioned aqueous ink compositions containing colorants, however,are extremely preferable because they can provide a glittering feelingdepending upon the hue or the like of the colorants contained.

The colorant is preferably contained in 0.01-30% by weight relative tothe total amount of the ink composition. When the colorant is less than0.01% by weight relative to the total amount of the ink composition,coloring by the colorant is difficult to be visually recognized. Whenthe colorant exceeds 30% by weight in the total amount of the inkcomposition, the viscosity of the ink becomes so high that the fluiditybecomes poor. The optimum amount of the colorant to be compounded, whichvaries depending on its type, ranges from 0.05-20% by weight.

(Water-soluble Resin)

As a water-soluble resin, preferably used is the water-solublethickening resin which is capable of dispersing the glass flake pigmentor the metal coated inorganic pigments and of preventing them fromprecipitation. Applicable as polysaccharides are microbialpolysaccharides and derivatives thereof, including pullulan, xanthangum, welan gum, rhamsan gum, succinoglucan and dextran; water-solublepolysaccharides derived from plants and derivatives thereof includingtragacanth gum, guar gum, tara gum, locust bean gum, ghatti gum,arabinogalactan gum, gum arabic, quince seed gum, pectin, starch,psyllium seed gum, pectin, carrageenan, alginic acid, agar and the like;water-soluble polysaccharides derived from animals and derivativesthereof including gelatin, casein and albumin. Moreover,N-vinylacetamide type resins such as N-vinylacetamide resin andcrosslinked N-vinylacetamide resin can be used as the thickening resin.

In the present invention, the microbial polysaccharides and derivativesthereof can specifically and preferably be used among the aforementionedwater-soluble resins. Such water-soluble resins can be used either aloneor in combinations of two or more of them.

The water-soluble resin is preferably contained in 0.01-40% by weightrelative to the total amount of the ink composition. If the content ofthe water-soluble resin is less than 0.01% by weight relative to thetotal amount of the ink composition, effect on preventing precipitationof the glass flake pigment or the metal coated inorganic pigment becomesunsatisfactory. When the water-soluble resin exceeds 40% by weightrelative to the total amount of the ink composition, the viscosity ofthe ink becomes so high that the fluidity becomes poor. The optimumamount of the water-soluble resin to be compounded, which variesdepending on its type, ranges 0.05-20% by weight.

(Synthetic Resin Emulsion)

As previously mentioned, the present inventors have found that in orderto obtain handwriting of metallic luster color such as gold and silverand the like, the use of glass flake pigments for ink compositionscontaining a water-soluble thickening resin, a water-soluble organicsolvent and water is preferable. The glass flake pigments can provide,to handwritings or coated films, glittering feeling and spatial effecthigher than those with aluminum powder pigments and pearlescentpigments.

However, they have also found that although an aqueous glittering inkcomposition containing a water-soluble thickening resin can increase thefixability of the glass flake pigments by this water-soluble thickeningresin, it is difficult to fix firmly to handwritings or coated filmssince the size of the glass flake pigment is large. Accordingly, in thecase of the aqueous ink composition containing glass flake pigments, theglass flake pigments are easily peeled by friction after writing orcoating and it is difficult to maintain high glittering feeling andspatial effect to handwritings or coated films. Therefore, thedurability of handwritings or coated films having glittering feeling andspatial effect becomes poor.

From the above-mentioned situation, an important problem is to provideaqueous glittering ink compositions which can improve the fixability ofglass flake pigments to handwritings or coated films and maintain ahigher glittering feeling and spatial effect for the handwritings orcoated films without deteriorating ink characteristics or writingcharacteristics and without inhibiting the effects on the highglittering feeling and spatial effect derived from compounding the glassflake pigments.

As a result of intensive studies for solving this problem, they havefound that the problem can be solved by aqueous glittering inkcompositions containing, as essential ingredients, a glass flakepigment, a water-soluble thickening resin, a water-soluble organicsolvent and water, and further containing a binder component which fixesthe glass flake pigment to handwritings or coated films.

On the other hand, another possible option for fixing such a glass flakepigment to handwritings or coated films is to use a water-solublesynthetic resin as a binder component. However, in the case of somewater-soluble synthetic resins, if the contents thereof are set to behigh in order to fix the glass flake pigment firmly, the solubility ofthe thickening resin and dispersibility of the colorant are badlyinfluenced. Moreover, there may be cases where viscoelasticity of theink are greatly reduced, which leads to reduction in writingcharacteristics. Moreover, even if fixability to handwritings or coatedfilms is shown, aqueous ink compositions should not be the ones whereinhigh glittering feeling and spatial effect of the glass flake pigmentare contained but are poor in handwritings or coated films.

The present inventors have made further intensive studies. As a result,they have found that the use of a synthetic resin emulsion as a bindercomponent for fixing the glass flake pigment to handwritings or coatedfilms permits improvement in fixability of the glass flake pigment tohandwritings or coated films without influencing the solubility ofwater-soluble thickening resins, dispersibility of colorants,viscoelasticity of ink, and coloring of ink and without inhibitingeffects of high glittering feeling and spatial effect by compounding theglass flake pigment, and they have accomplished the present invention.

Accordingly, the aqueous ink composition of the present invention whichcontains a glass flake pigment is capable of improving the fixability ofthe glass flake pigment to handwritings or coated films, forminghandwritings or coated films of durability, and maintaining a highglittering feeling and spatial effect for the handwritings or coatedfilms when it is put on a substrate such as paper, metal, plastics andtextile fabrics by writing or coating. The reason for this is that thefilm formability of the synthetic resin emulsion is suitable for glassflake pigments having a large-sized flake shape and the glass flakepigment can be fixed firmly to handwritings or coated films withoutinhibiting the effects of high glittering feeling and spatial effect bycompounding the glass flake pigment.

Moreover, since the binder component used in the present invention isnot a water-soluble synthetic resin but a synthetic resin emulsion, itdoes not influence properties including solubility of the water-solublethickening resin to be compounded together, dispersibility of thecolorant and viscoelasticity of the ink very much. The ink compositionof the present invention therefore can improve the fixability of theglass flake pigment without influencing the viscoelasticity of the ink,writing characteristics and color of handwritings or coated films.

From such facts, the aqueous glittering ink composition of the presentinvention containing the glass flake pigment can maintain, inhandwritings or coated films, a glittering feeling and spatial effecthigher than those achieved by the conventional aqueous ink compositionsusing glittering pigments such as aluminum powder pigments andpearlescent pigments without deteriorating ink characteristics, writingperformance or the like or without inhibiting the high surfacesmoothness inherent to glass.

The synthetic resin emulsion of the present invention is notspecifically limited and any water-dispersive synthetic resin emulsionis available. Considering the ink characteristics and writingperformance however, it is important to use the ones which do notinfluence solubility of water-soluble thickening resin, viscosity of theink, dispersibility of the colorant and coloring of the ink. Moreover,it is important not to inhibit the effect on the high glittering feelingand spatial effect caused by the composition of the glass flake pigment.

The minimum film forming temperature of the synthetic resin emulsion ispreferably not higher than 20° C. If the minimum film formingtemperature of the synthetic resin emulsion is not higher than 20° C.,particularly not higher than 0° C., a film can be formed not only atroom temperature (about 25° C.) but in a cold district and fixability ofhandwritings or coated films to substrates can be improved.

Synthetic resin emulsions having an anionic property or a nonionicproperty preferably can be used. Such synthetic resin emulsions havingthe anionic property or the nonionic property can be prepared, forexample, by producing synthetic resins from anionic or nonionic monomersor using anionic or nonionic emulsifiers. If the synthetic resinemulsion has the anionic property or the nonionic property, thestability of the ink composition can be improved.

Preferred synthetic resin emulsions do not influence the dispersibilityof colorants or solubility of water-soluble thickening resin when the pHof inks are 6 or more.

From such a viewpoint, for example, acryl based synthetic resinemulsions, styrene-acryl based synthetic resin emulsions and vinylacetate based synthetic resin emulsions can be used as a synthetic resinemulsion. Preferred examples of the acryl based synthetic resins includeacrylate copolymer synthetic resin emulsions. Preferred examples of thestyrene-acryl based synthetic resin emulsions include styrene-acrylatecopolymer synthetic resin emulsions. As the vinyl acetate basedsynthetic resin emulsions, vinyl acetate synthetic resin emulsions andvinyl acetate-acrylate copolymer synthetic resin emulsions, for example,are preferably used. As the synthetic resin emulsion, one species ofthese synthetic resins can be used and also two or more species of thesesynthetic resins can be used in combination.

For example, the acryl based synthetic resin emulsion can be exemplifiedby the trade name “Nikasol FX336” (manufactured by Nippon CarbideIndustries Co., Inc.; anionic; pH 7.5; minimum film formingtemperature=0° C.), the trade name “Mowinyl DM772” (manufactured byClariant Polymers Co., Ltd; anionic; pH 8.5; minimum film formingtemperature=12-14° C.) and the trade name “Mowinyl 700” (manufactured byClariant Polymers Co., Ltd; anionic; pH 8.0; minimum film formingtemperature=5° C.). The vinyl acetate based synthetic resin emulsion canbe exemplified by the trade name “Nikasol TG134A” (manufactured byNippon Carbide Industries Co., Inc.; pH 7.5; minimum film formingtemperature=0° C.) and the trade name “Mowinyl 507” (manufactured byClariant Polymers Co., Ltd; nonionic; pH 6.5; minimum film formingtemperature=0° C.).

Although the content of the synthetic resin emulsion is not particularlyspecified, a preferable range is 0.01-40% by weight in solids relativeto the total amount of the ink composition, for example. The content ofthe synthetic resin emulsion of less than 0.01% by weight in solidsrelative to the total amount of the ink composition results in reductionin fixability of the glass flake pigment to handwritings or coatedfilms. If the content of the synthetic resin emulsion exceeds 40% byweight in solids relative to the total amount of the ink composition,the solids are so high that writing characteristics are deterioratedbecause of, for example, film formation at the pen tip. In addition,handwritings or coated films are liable to whiten. In order to improvethe fixability of the glass flake pigment to handwritings or coatedfilms further, the most desirable content of the synthetic resinemulsion is at least 0.3% by weight in solids relative to the totalamount of the ink composition. Moreover, in order to improve writingcharacteristics further, the most desirable content of the syntheticresin emulsion is 20% by weight in solids relative to the total amountof the ink composition. That is, the optimum content of the syntheticresin emulsion is 0.3-20% by weight.

In addition, also in the case of the ink composition containing thesynthetic resin emulsion as a binder component together with the glassflake pigment, it is important that the resins can adjust viscosity ofthe ink and facilitate dispersion of the glass flake pigment and preventits precipitation. Water-soluble thickening resin with a function toform a film of handwritings or coated films can be used. For example,microbial polysaccharides and derivatives thereof can be used, includingpullulan, xanthan gum, welan gum, rhamsan gum, succinoglucan anddextran. Water-soluble polysaccharides derived from plants andderivatives thereof also can be used, including tragacanth gum, guargum, tara gum, locust bean gum, ghatti gum, arabinogalactan gum, gumarabic, quince seed gum, pectin, starch, psyllium seed gum, pectin,carrageenan, alginic acid and agar. Water-soluble polysaccharidesderived from animals and derivatives thereof can also be used, includinggelatin, casein and albumin.

As the water-soluble thickening resin, salts (sodium salts, ammoniumsalts and the like) of water-soluble resins (acryl based water-solubleresins, styrene-acryl based resins, styrene-maleic acid based resins andthe like), water-dispersion type resins and the like can also be used.

In the case of ink compositions which contain a synthetic resin emulsionas a binder component together with the glass flake pigment, themicrobial polysaccharides and derivatives thereof can be used preferablyamong the aforementioned water-soluble thickening resins. Suchwater-soluble thickening resins can be used either alone or incombinations of two or more of them.

In the case of ink compositions which contain a synthetic resin emulsionas a binder component together with the glass flake pigment, thewater-soluble thickening resin is preferably contained in 0.01-40% byweight relative to the total amount of the ink composition. In the casewhere the water-soluble thickening resin is less than 0.01% by weightrelative to the total amount of the ink composition, the glass flakepigment is liable to precipitate. If the water-soluble thickening resinexceeds 40% by weight relative to the total amount of the inkcomposition in the case of the ink composition containing the syntheticresin emulsion, the viscosity of the ink becomes so high that thefluidity becomes poor and writing characteristics are deteriorated. Theoptimum amount of the water-soluble thickening resin to be compoundedsomewhat varies depending upon the type of the water-soluble thickeningresin, but is 0.05-20% by weight.

Also in the case of the ink composition containing a synthetic resinemulsion as a binder component, water-soluble organic solvents which arecapable of preventing both drying at the pen tip and freezing of the inkare preferably used, which can be exemplified by glycols such asethylene glycol, diethylene glycol, triethylene glycol, propylene glycoland polyethylene glycol, polyhydric alcohols such as glycerin, andglycol ethers such as ethylene glycol monomethyl ether, diethyleneglycol monomethyl ether, dipropylene glycol monomethyl ether anddipropylene glycol monopropyl ether, and the like. These organicsolvents can be used either alone or in combination of two or more ofthem.

As for water-soluble organic solvents, aliphatic monohydric alcoholswith 1 to 4 carbon atoms, aliphatic polyhydric alcohols such asglycerin, glycols such as propylene glycol and glycol ethers such aspropylene glycol monomethyl ether and the like are preferably used.

Also in the case of the ink composition containing the synthetic resinemulsion as a binder component together with the glass flake pigment,the content of the water-soluble organic solvent is 1-40% by weightrelative to the total amount of the ink composition. In the case wherethe content of the water-soluble organic resin is less than 1% by weightrelative to the total ink composition, a pen tip is liable to dry andthe ink becomes liable to freeze. If the content of the water-solubleorganic solvent exceeds 40% by weight relative to the total amount ofthe ink composition, the solubility of the water-soluble thickeningresin is influenced and handwritings and coated films become hard todry. In the case of this ink composition, the optimum amount of thewater-soluble organic solvent to be compounded varies depending upon thetype of the water-soluble organic solvent, but is 5-30% by weight.

Also in the case of the ink composition containing the synthetic resinemulsion as a binder component together with the glass flake pigment,colorants can be used. The use of colorants-can adjust the color of theink to various colors. It is important to use colorants which do notreact with the glass flake pigments and do not influence the coloring ofthe glass flake pigments. Moreover, the one excellent in solubility anddispersibility are preferable as a colorant.

For example, water-soluble dyes such as acid dyes, direct dyes and basicdyes (triphenylmethane-type, xanthene-type, anthraquinone-type, metalcomplex-type, copper phthalocyanine-type and the like), organic pigmentsor inorganic solvents such as phthalocyanine, quinacridone, carbon blackand titanium oxide, or fluorescent pigments, resin emulsions, coloredresin emulsion and the like can be used. The colorant also can becompounded in the form of a pigment dispersion. The colorants can beused either alone or in combinations of two or more of them.

Also in the case of the ink composition containing the synthetic resinemulsion together with the glass flake pigment, colorants need not becontained. Even aqueous ink compositions containing not colorants butglass flake pigments can add a high glittering feeling and high spatialeffect to handwritings or coated films. Each of the aforementionedaqueous ink compositions containing colorants, however, is extremelypreferable because they can provide high brilliance depending upon thehue or the like of the colorants contained.

In the case of the ink composition containing the synthetic resinemulsion as a binder component together with the glass flake pigment,the content of the colorant is preferably 0.01-30% by weight relative tothe total amount of the ink composition. When the colorant is less than0.01% by weight relative to the total amount of the ink composition, thecoloring by the colorant becomes difficult to be visually recognized.When the colorant exceeds 30% by weight relative to the total amount ofthe ink composition, the viscosity of the ink becomes so high that thefluidity becomes poor and glittering feeling is deteriorated. Theoptimum amount of the colorant to be compounded, which varies dependingon its type, is 0.05-20% by weight.

(Other Additives)

Moreover, to the ink composition of the present invention can becompounded conventional water such as ion-exchange water. In addition,as needed, lubricants such as polyoxyethylene alkali metal salts,dicarboxylic amides, phosphates and N-oleyl sarcosine salts and thelike, rust-inhibitors such as benzotriazole and tolyltriazoledicyclohexyl ammonium nitrate and the like, antiseptic mildew-proofingagents such as benzoisothiazoline-type, pentachlorophenol-type andcresol and the like, and various surfactants can be added.

(Viscosity Range)

The preferred viscosity range of the ink composition is 1000-10000mPa.s. The ink composition of the present invention is adjusted to sucha viscosity range. These viscosities are measured values by an ELD-typeviscometer (3° R14 corn; rotation speed: 0.5 rpm; 20° C.).

(Applications)

The aqueous glittering ink composition can be used in the fields ofwriting tools, printing, coating and cosmetics and the like. It isuseful in a variety of applications as an aqueous glittering inkcomposition for writing tools (an aqueous glittering ink composition forball-point pens and the like), an aqueous glittering ink composition forprinting, an aqueous glittering ink composition for applicators (anaqueous glittering ink composition for coating and the like) and thelike. It is particularly the most desirable as an aqueous glittering inkcomposition for ball-point pens.

(Method of Preparation)

The aqueous glittering ink composition of the present invention is notspecifically limited but can be obtained, for example, by mixing andstirring ingredients such as water, a water-soluble organic solvent, aglass flake pigment and a colorant or a pigment base to disperse them,and thereafter charging a water-soluble resin and filtering theresulting mixture, and subsequently degassing. In particular, the inkcomposition containing the synthetic resin emulsion as a bindercomponent together with the glass flake pigment is preferably preparedby the following process, although the preparation is not specificallylimited. First, water, a water-soluble organic solvent, and, as needed,other additives are mixed and stirred; to the mixture is charged theglass flake pigment, and the resulting mixture is stirred; andthereafter a water-soluble thickening resin is added and stirred. Next,the pH of the mixed liquid is adjusted as needed, and a colorant isadded and stirred, as needed. Subsequently, the synthetic resin emulsionis added and mixed.

As for these preparations, heretofore known dispersing techniques,degassing techniques, filtering techniques and the like can be adopted.

EXAMPLES

Aqueous glittering ink compositions of the Examples provided by mixingand stirring ingredients including water, a water-soluble organicsolvent, a glass flake pigment and a colorant or a pigment base and thelike in the compositions and amounts (parts by weight) given in Table 1to disperse them, thereafter charging a water-soluble resin andfiltering the resulting mixture, and subsequently degassing. Forcomparison, aqueous glittering ink compositions of the ComparativeExamples were prepared by mixing and stirring ingredients includingwater, a water-soluble organic solvent, a glittering pigment and thelike to disperse them, thereafter charging a water-soluble resin andfiltering the resulting mixture, and subsequently degassing. In everypreparation, heretofore known dispersing, degassing, filteringtechniques and the like were used.

Likewise, aqueous glittering ink compositions of other Examples andComparative Examples were prepared by mixing and stirring ingredientsincluding water, a water-soluble organic solvent and a glitteringpigment and the like in the compositions and amounts (parts by weight)given in Table 2 to disperse them, thereafter charging a water-solubleresin and filtering the resulting mixture, and subsequently degassing.In every preparation, heretofore known dispersing, degassing, filteringtechniques and the like were used.

In the same manner as previously mentioned, aqueous glittering inkcompositions of other Examples and Comparative Examples were prepared bymixing and stirring ingredients including a glass flake pigment orbrilliant pigment, water, a water-soluble organic solvent and the likein the compositions and amounts (parts by weight) given in Tables 3-8 todisperse them, thereafter charging a water-soluble resin and filteringthe resulting mixture, and subsequently degassing. In every preparation,heretofore known dispersing, degassing, filtering techniques and thelike were used.

For information, a colored emulsion containing a fluorescent pigment isused as a colorant in Examples in Table 6.

TABLE 1 (Parts by weight) Comparative Examples Examples 1 2 3 4 5 1 2Glass flake {circle around (1)} 7.0 — 7.0 — — — — pigment {circle around(2)} — 5.0 — 5.0 10.0  — — Glittering {circle around (1)} — — — — — 5.0— pigment {circle around (2)} — — — — — — 10.0  Water-soluble {circlearound (1)} 0.3 0.3 — — — 0.3 — resin {circle around (2)} — — 0.3 0.30.2 — 0.3 Colorant {circle around (1)} 1.0 1.0 — — — — — {circle around(2)} — — — — 2.0 — — Pigment base {circle around (1)} — — 20.0  20.0  —— — Water-soluble {circle around (1)} 5.0 5.0 5.0 5.0 — 5.0 5.0 organicsolvent {circle around (2)} — — — — 7.0 — — {circle around (3)} — — — —14.0  — — Antiseptic {circle around (1)} 0.1 0.1 0.1 0.1 0.1 0.1 0.1mildew-proofing agent Rust-inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 0.1Lubricant 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Water 85.3  87.3  66.3  68.3 65.4  88.3  83.3  Evaluation test Glittering feeling ◯ ◯ ◯ ◯ ◯ X XSpatial effect ◯ ◯ ◯ ◯ ◯ X X Writing performance ◯ ◯ ◯ ◯ ◯ ◯ ◯

TABLE 2 (Parts by weight) Comparative Examples Examples 6 7 8 9 10 3Glittering {circle around (3)} 7.0 — 7.0 — 7.0 — pigment {circle around(4)} — 5.0 — 5.0 — — {circle around (1)} — — — — — 7.0 Water-soluble{circle around (1)} 0.3 0.3 — — — — resin {circle around (2)} — — 0.30.3 0.2 0.3 {circle around (3)} — — — — — 3.0 Water-soluble {circlearound (1)} 5.0 5.0 5.0 5.0 — 5.0 organic solvent {circle around (2)} —— — — 7.0 {circle around (3)} — — — — 14.0 — Colorant {circle around(2)} — — — — 2.0 — Pigment base {circle around (2)} — — — — — 40.0 Antiseptic {circle around (1)} 0.1 0.1 0.1 0.1 0.1 0.1 mildew-proofingagent Rust-inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 Lubricant 1.2 1.2 1.2 1.21.2 1.2 Water 86.3  88.3  86.3  88.3  68.4  43.3  Evaluation testGlittering feeling ◯ ◯ ◯ ◯ ◯ X Writing performance ◯ ◯ ◯ ◯ ◯ ◯

TABLE 3 (Parts by weight) Examples 11 12 13 14 15 Glass flake {circlearound (3)} 7.0 — 7.0 — — pigment {circle around (4)} — 5.0 — 5.0 10.0 Water-soluble {circle around (1)} 0.3 0.3 — — — resin {circle around(2)} — — 0.3 0.3 0.2 Colorant {circle around (1)} 1.0 1.0 — — — {circlearound (2)} — — — — 2.0 Pigment base {circle around (1)} — — 20.0  20.0 — Water-soluble {circle around (1)} 5.0 5.0 5.0 5.0 — organic solvent{circle around (2)} — — — — 7.0 {circle around (3)} — — — — 14.0 Antiseptic {circle around (1)} 0.1 0.1 0.1 0.1 0.1 mildew-proofing agentRust-inhibitor 0.1 0.1 0.1 0.1 0.1 Lubricant 1.2 1.2 1.2 1.2 1.2 Water85.3  87.3  66.3  68.3  65.4  Evaluation test Glittering feeling ◯ ◯ ◯ ◯◯ Spatial effect ◯ ◯ ◯ ◯ ◯ Writing performance ◯ ◯ ◯ ◯ ◯

TABLE 4 (Parts by weight) Comparative Examples Examples 16 17 18 19 4 5Glass flake {circle around (1)} 0.01 — — 40.0   0.005 50.0  pigment{circle around (4)} — 0.5 30.0  — — — Water-soluble {circle around (1)}0.3 0.3 — — 0.3 0.3 resin {circle around (2)} — — 0.3 0.3 — — Colorant{circle around (1)} 1.0 1.0 1.0 2.0 — 2.0 Water-soluble {circle around(1)} 5.0 5.0 5.0 5.0 5.0 5.0 organic solvent Antiseptic {circle around(1)} 0.1 0.1 0.1 0.1 0.1 0.1 mildew-proofing agent Rust-inhibitor 0.10.1 0.1 0.1 0.1 0.1 Lubricant 1.2 1.2 1.2 1.2 1.2 1.2 Water 92.29 91.8 92.3  51.3   93.295 41.3  Evaluation test Glittering feeling ◯ ◯ ◯ ◯ X ◯Spatial effect ◯ ◯ ◯ ◯ X ◯ Writing performance ◯ ◯ ◯ ◯ ◯ X

TABLE 5 (Parts by weight) Comparative Examples Examples 20 21 22 23 6 7Glittering {circle around (3)}  0.01 — — 40.0   0.005 50.0  pigment{circle around (4)} — 0.5 30.0  — — — Water-soluble {circle around (1)}0.3 0.3 — — 0.3 0.3 resin {circle around (2)} — — 0.3 0.3 — —Water-soluble {circle around (1)} 5.0 5.0 5.0 5.0 5.0 5.0 organicsolvent Antiseptic {circle around (1)} 0.1 0.1 0.1 0.1 0.1 0.1mildew-proofing agent Rust-inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 Lubricant1.2 1.2 1.2 1.2 1.2 1.2 Water 93.29 92.8  63.3  53.3   93.295 43.3 Evaluation test Glittering feeling ◯ ◯ ◯ ◯ X ◯ Writing performance ◯ ◯ ◯◯ ◯ X

TABLE 6 (Parts by weight) Examples 24 25 26 27 28 29 30 Glass flake{circle around (1)} 5.0 5.0 — — — — — pigment {circle around (2)} — —5.0 — — — — {circle around (3)} — — — 5.0 — — — {circle around (4)} — —— — 5.0 — — Glittering {circle around (3)} — — — — — 5.0 — pigment{circle around (4)} — — — — — — 5.0 Water-soluble {circle around (1)}0.3 0.3 — — — 0.3 — resin {circle around (2)} — — 0.3 0.3 0.3 — 0.3Colorant {circle around (5)} 1.0 — 1.0 1.0 — 1.0 1.0 {circle around (6)}— 1.0 — — 1.0 — — Water-soluble {circle around (1)} 5.0 5.0 5.0 5.0 5.05.0 5.0 organic solvent Antiseptic {circle around (1)} 0.1 0.1 0.1 0.10.1 0.1 0.1 mildew-proofing agent Rust-inhibitor 0.1 0.1 0.1 0.1 0.1 0.10.1 Lubricant 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Water 87.3  87.3  87.3  87.3 87.3  87.3  87.3  Evaluation test Glittering feeling ◯ ◯ ◯ ◯ ◯ ◯ ◯Spatial effect ◯ ◯ ◯ ◯ ◯ — — Writing performance ◯ ◯ ◯ ◯ ◯ ◯ ◯

TABLE 7 (Parts by weight) Examples 31 32 33 34 Glass flake {circlearound (1)} 7.0 — 7.0 — pigment {circle around (2)} — 5.0 — 5.0Glittering {circle around (1)} — — — — pigment {circle around (2)} — — —— Water-soluble {circle around (4)} 0.3 — 0.2 resin {circle around (5)}— 0.3 0.1 {circle around (6)} 0.3 Colorant {circle around (1)} 1.0 1.0 —— {circle around (2)} — — — — Pigment base {circle around (1)} — — 20.0 20.0  Water-soluble {circle around (1)} 5.0 5.0 5.0 5.0 organic solvent{circle around (2)} — — — — {circle around (3)} — — — — Antiseptic{circle around (1)} 0.1 0.1 0.1 0.1 mildew-proofing agent Rust-inhibitor0.1 0.1 0.1 0.1 Lubricant 1.2 1.2 1.2 1.2 Water 85.3  87.3  66.3  68.3 Evaluation test Glittering feeling ◯ ◯ ◯ ◯ Spatial effect ◯ ◯ ◯ ◯Writing ◯ ◯ ◯ ◯ performance

TABLE 8 (Parts by weight) Examples 35 36 37 38 39 40 Glass flake {circlearound (1)} 5.0 5.0 5.0 — — — pigment {circle around (2)} — — — 5.0 5.05.0 Glittering {circle around (1)} 5.0 — — 5.0 — — pigment {circlearound (2)} — 5.0 — — 5.0 — Water-soluble {circle around (1)} 0.3 0.30.3 0.3 0.3 0.3 resin Pigment base {circle around (3)} — — 20.0  — —20.0  Water-soluble {circle around (1)} 5.0 5.0 5.0 5.0 5.0 5.0 organicsolvent Antiseptic {circle around (1)} 0.1 0.1 0.1 0.1 0.1 0.1mildew-proofing agent Rust-inhibitor 0.1 0.1 0.1 0.1 0.1 0.1 Lubricant1.2 1.2 1.2 1.2 1.2 1.2 Water 83.3  83.3  68.3  83.3  83.3  68.3 Evaluation test Glittering feeling ◯ ◯ ◯ ◯ ◯ ◯ Spatial effect ◯ ◯ ◯ ◯ ◯◯ Writing performance ◯ ◯ ◯ ◯ ◯ ◯

Example 41

An aqueous glittering ink composition of Example 41 was obtained in thecomposition and amounts (parts by weight) given in Table 9 by thefollowing method of preparation with regard to compounding of thesynthetic resin emulsion. That is, water, a water-soluble organicsolvent and, as needed, other additives are mixed and stirred; a glassflake pigment is charged to the resultant and stirred; and thereafter awater-soluble thickening resin is added and stirred. Next, the pH of themixed liquid is adjusted as needed, and a colorant is added and stirredas needed. Subsequently, a synthetic resin emulsion is added and mixed.

In this preparation, heretofore known dispersing, degassing, filteringtechniques and the like were adopted. In the foregoing producingprocess, the pH was adjusted to 8.5 with caustic soda.

Examples 42-49

Aqueous glittering ink compositions of Examples 42-49 were prepared inthe same manner as Example 41 except for using the compositions andamounts (parts by weight) given in Tables 9 and 10.

Comparative Examples 8-14

Aqueous glittering ink compositions of Comparative Examples 8-14 wereprepared in the same manner as Example 41 except for using thecompositions and amounts Warts by weight) given in Tables 9 and 10.

For information, in Examples 42-49 and Comparative Examples 8-14 used,heretofore known dispersing, degassing, filtering techniques and thelike were adopted.

TABLE 9 (Parts by weight) Comparative Examples Examples 41 42 43 44 45 89 10 Glass {circle around (4)} 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 flakepigment Water- {circle around (4)} 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2soluble {circle around (5)} 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 thickeningresin Binder {circle around (1)} 7.5 com- {circle around (2)} 7.5 ponent{circle around (3)} 7.5 (solids) {circle around (4)} 7.5 {circle around(5)} 7.5 {circle around (6)} 2.0 15.0  Water- {circle around (1)} 7.07.0 7.0 7.0 7.0 7.0 7.0 7.0 soluble {circle around (4)} 15.0  15.0 15.0  15.0  15.0  15.0  15.0  15.0  organic solvent Pigment {circlearound (1)} 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 base Antiseptic {circlearound (1)} 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 mildew- proofing agentLubricant 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water 63.0  63.0  63.0  63.0 63.0  70.5  68.5  55.5  Fixability ◯ ◯ ◯ ◯ ◯ X X ◯ Writing ◯ ◯ ◯ ◯ ◯ ◯ ◯X aptitude Glittering ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ feeling Spatial effect ◯ ◯ ◯ ◯ ◯ ◯◯ ◯ Note) The binder component is indicated by a content of solids(parts by weight).

TABLE 10 (Parts by weight) Examples Comparative Examples 46 47 48 49 1112 13 14 Glass flake {circle around (4)} 5.0 0.5 30 5.0 5.0 5.0 0.005 50pigment Water-soluble {circle around (4)} 0.2 0.2 0.2 0.2 0.2 0.2 0.20.2 thickening resin {circle around (5)} 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1Binder component {circle around (1)} 40 0.01 0.005 45 (solids) {circlearound (2)} 7.5 7.5 7.5 7.5 Water-soluble {circle around (1)} 7.0 7.07.0 7.0 7.0 7.0 7.0 7.0 organic solvent {circle around (4)} 15.0  15.0 15.0  15.0  15.0  15.0  15.0  15.0  Pigment base {circle around (1)} 2.02.0 2.0 2.0 2.0 2.0 2.0 2.0 Antiseptic {circle around (1)} 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 mildew-proofing agent Lubricant 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 Water 30.5 67.5 38.0 70.49 70.495 25.5 67.995 18.0Fixability ◯ ◯ ◯ ◯ X ◯ ◯ ◯ Writing aptitude ◯ ◯ ◯ ◯ ◯ X ◯ X Glitteringfeeling ◯ ◯ ◯ ◯ ◯ X X ◯ Spatial effect ◯ ◯ ◯ ◯ ◯ X X ◯ Note) The bindercomponent is indicated by a content of solids (parts by weight).

In Tables 1-10, each raw material composition is as follows:

(Glass Flake Pigment)

{circle around (1)} Trade name “Crystal Color GF2525-M”, manufactured byToyo Aluminium Co., Ltd., median diameter=about 25 μm

{circle around (2)} Trade name “Crystal Color GF2540”, manufactured byToyo Aluminium Co., Ltd., median diameter=about 40 μm

{circle around (3)} Trade name “Metashine REFSX-2025PS”, manufactured byToyo Aluminium Co., Ltd., median diameter=about 25 μm

{circle around (4)} Trade name “Metashine REFSX-2040PS”, manufactured byToyo Aluminium Co., Ltd., median diameter=about 40 μm

(Glittering Pigment)

{circle around (1)} Aluminum powder pigment: trade name “WXM0630”,manufactured by Toyo Aluminium Co., Ltd., average particle size=about 8μm

{circle around (2)} Pearlescent pigment: trade name “Iriodin 302”,manufactured by Merck Japan Limited, average particle size=about 5-20 μm

{circle around (3)} Metal coated inorganic pigment (yellow): trade name“Paliocrom Gold L2002”, manufactured by BASF AG, median diameter=about20 μm

{circle around (4)} Metal coated inorganic pigment (yellow): trade name“Paliocrom Gold L2022”, manufactured by BASF AG, median diameter=about16 μm

(Water-soluble Resin)

{circle around (1)} Rhamsan gum: trade name “K7C233”, manufactured bySansho Co., Ltd

{circle around (2)} Welan gum: trade name “K1C376”, manufactured bySansho Co., Ltd

{circle around (3)} Carboxymethyl cellulose (CMC): trade name “Cellogen7A”, number average molecular weight=27000-33000, manufactured byDai-ichi Kogyo Seiyaku Co., Ltd.

{circle around (4)} Xanthan gum: trade name “Kelzan”, manufactured byKelco a unit of Monsanto Company.

{circle around (5)} Polyacrylic acid: trade name “Carbopol 940”,manufactured by BF Goodrich Co., Ltd.

{circle around (6)} Succinoglycan: trade name “Reozan”, manufactured bySansho Co., Ltd

(Water-soluble Organic Solvent)

{circle around (1)} Glycerin

{circle around (2)} Dipropylene glycol monopropyl ether

{circle around (3)} Dipropylene glycol monomethyl ether

{circle around (4)} Propylene glycol

(Colorant)

{circle around (1)} Yellow dye: trade name “Yellow 202 (1)”, Acid Yellow73, Aizen Co., Ltd.

{circle around (2)} Red dye: trade name “Chugai Aminol First pink R”,xanthen-type, manufactured by Chugai Kasei Co., Ltd.

{circle around (3)} Blue pigment: trade name “Firstgen Blue TGR”,phthalocyanine blue, manufactured by Dainippon Ink & Chemicals, Inc.

{circle around (4)} Yellow pigment: trade name “Seikafast Yellow A-3”,azo-type, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

{circle around (5)} Yellow resin emulsion: trade name “LUMIKOLNKW-2105”, yellow fluorescent pigment, manufactured by Nippon KeikoKagaku CO., Ltd.

{circle around (6)} Blue resin emulsion: trade name “LUMIKOL NKW-2108”,blue fluorescent pigment, manufactured by Nippon Keiko Kagaku CO., Ltd.

{circle around (7)} White pigment: trade name “Kronos-KR380”, titaniumoxide, manufactured by Titan Kogyo CO., LTD.

(Pigment Base)

{circle around (1)} Pigment base: A pigment dispersion of a pigment basewas obtained, in the form of a water dispersion of pigment (averageparticle size=0.08 μm; solid content=10% by weight), by adding anddissolving triethylamine to a mixture obtained by mixing theabove-mentioned blue pigment {circle around (3)} and the following resinfor dispersing pigment in the following proportion, and thereafterconducting dispersion with a ball mill. As the resin for dispersingpigment a styrene-acryl copolymer was used (trade name “JOHNCRYL J683”,Johnson Polymer Co., Ltd., weight average molecular weight=8000).

Blue pigment {circle around (3)} 5 parts by weight Resin for dispersingpigment 1 part by weight

{circle around (2)} Pigment base: A pigment dispersion of a pigment basewas obtained, in the form of a water dispersion of pigment (averageparticle size=0.08 μm; solid content=10% by weight), by adding anddissolving triethylamine to a mixture obtained by mixing theabove-mentioned yellow pigment {circle around (4)} and the followingresin for dispersing pigment in the following proportion, and thereafterconducting dispersion with a ball mill. As the resin for dispersingpigment was used a styrene-acryl copolymer (trade name “JOHNCRYL J683”,Johnson Polymer Co., Ltd., weight average molecular weight=8000).

Yellow pigment {circle around (4)} 5 parts by weight Resin fordispersing pigment 1 part by weight

{circle around (3)} Pigment base: A pigment dispersion of a pigment basewas obtained, in the form of a water dispersion of pigment (averageparticle size=0.4 μm; solid content=10% by weight), by adding anddissolving triethylamine to a mixture obtained by mixing theabove-mentioned white pigment {circle around (7)} and the followingresin for dispersing pigment in the following proportion, and thereafterconducting dispersion with a ball mill. As the resin for dispersingpigment is used a styrene-acryl copolymer (trade mane “JOHNCRYL J683”,Johnson Polymer Co., Ltd., weight average molecular weight=8000).

White pigment {circle around (7)} 5 parts by weight Resin for dispersingpigment 1 part by weight (Antiseptic mildew-proofing agent)

{circle around (1)} 1,2-Benzoisothiazolin-3-one (trade name “ProxellGXL”, Hoechst Synthesis Co., Ltd.)

(Rust-inhibitor)

Benzotriazole

(Lubricant)

Maleic monoamide

(Preparation of Test Samples)

Next, each of the ink compositions of Examples and Comparative Examplesgiven in Tables 1-10 was packed into an ink container made of a hollowpolypropylene tube equipped with a ball-point pen tip made of stainlesssteel (ball material: silicon carbide), and ball-point pens of testsamples having the ink containers therein were prepared.

(Evaluation Test)

The glittering feeling and spatial effect of each ink composition forthe Examples and Comparative Examples given in Table 1 and theglittering feeling of each ink composition for the Examples andComparative Examples given in Table 2 were evaluated by writing oncommercially available loose-leaf sheets with these ball-point pens. Theglittering feeling and spatial effect of each ink for the Examples andComparative Examples given in Tables 3-4, the glittering feeling of eachink for the Examples and Comparative Examples given in Table 5, theglittering feeling and spatial effect of the ink for Example 28 given inTable 6 and the glittering feeling of each ink for Examples 29 and 30given in Table 6 were evaluated. The glittering feeling and spatialeffect of each ink wherein other water-soluble resins were incorporatedwere evaluated for Examples 31-34 given in Table 7. The glitteringfeeling and spatial effect of each ink were evaluated for Examples 35-40given in Table 8. Also, the writing performance was evaluated for eachExample and each Comparative Example given in Tables 1-8. The glitteringfeeling, spatial effect and furthermore fixability and writing aptitudewere evaluated for each ink of Examples 41-49 containing resin emulsionsgiven in Tables 9 and 10.

(Evaluation of Glittering Feeling)

Evaluation of the glittering feeling was conducted by visual observationof writings. Rating criteria were: ∘ for ones having strong glitteringfeeling; X for ones having little or no glittering feeling.

(Evaluation of Spatial Effect)

Evaluation of the spatial effect also was conducted by visualobservation. Rating criteria were: ∘ for ones having spatial effect; Xfor ones having no spatial effect.

(Evaluation of Writing Performance)

The writing performance was evaluated according to feeling in writing.Rating criteria were: ∘ for ones having good writing performance andpermitting smooth writing; X for ones having poor writing performanceand not permitting smooth writing very much.

(Test of Fixability)

The fixability shown in Tables 9 and 10 was evaluated according to thefollowing criteria by writing on commercially available loose-leafsheets with ball-point pens of test samples according to every Exampleand Comparative Example, drying the handwritings, thereafter adheringcommercially available adhesive cellophane tapes thereon, and thenvisually observing conditions after peeling the tapes.

∘: A glass flake pigment remains on the handwriting and the glitteringfeeling before peeling of the cellophane tape has not been lost.

X: A glass flake pigment is peeled from the handwriting and theglittering feeling before peeling of the cellophane tape has been lost.

(Test of Writing Characteristics)

The writing characteristics shown in Tables 9 and 10 were evaluated bywriting on commercially available loose-leaf sheets with ball-point pensof test samples according to every Example and Comparative Example, andrating writing feeling according to the following criteria.

∘: Writing feeling is smooth.

X: Writing feeling is heavy and the ink does not flow. A double-linehandwriting was obtained.

Tables 1-10 show results of glittering feeling, spatial effect andwriting performance in each Example and each Comparative Example.

From Table 1, Examples 1 and 2 provided handwritings having both astrong glittering feeling like sunshine and strong spatial effect.Examples 3 and 4 provided handwritings having a strong glitteringfeeling like stars twinkling in the night sky and strong spatial effect.Example 5 provided a coated film with a glittering feeling and spatialeffect inside and a double-colored red handwriting outside. On the otherhand, Comparative Examples 1 and 2 provided handwritings having weakglittering feeling but having no spatial effect. Writing performances ofthe inks of Examples 1-5 were good as in Comparative Examples 1 and 2.

From Table 2, Examples 6-9 containing metal coated inorganic pigments asglittering pigments provided golden handwritings with strong glitteringfeeling. Likewise, Example 10 containing a metal coated inorganicpigment as a glittering pigment provided a coated film having glitteringfeeling inside and a double-colored red handwriting. On the other hand,Comparative Example 3 containing an aluminum powder pigment as aglittering pigment provided a golden metallic handwriting having poorand weak glittering feeling. Writing performances of the inks ofExamples 6-10 were good as in Comparative Example 3.

The ink compositions of Examples 1-5 containing glass flake pigments canprovide handwritings with an unprecedented unique feeling since theseink compositions can provide handwritings with both a strong glitteringfeeling and strong spatial effect by comprising glass flake pigments andcolorants instead of using glittering pigments as in ComparativeExamples 1-2.

The ink compositions of Examples 6-10 cannot provide strong spatialeffect but can provide handwritings or coated films having a strongglittering feeling without loosing glitter in comparison to the inkcomposition of Comparative Example 3.

From Table 3, the inks of Examples 11 and 12 provided handwritingshaving a strong glittering feeling like sunshine and strong spatialeffect as in the inks of Examples 1 and 2. The inks of Examples 13 and14 provided handwritings having a strong glittering feeling like starstwinkling in the night sky and strong spatial effect as in the inks ofExamples 3 and 4. The ink of Example 15 provided a glittering coatedfilm inside and a double-colored red handwriting outside as in the inkof Example 10. The inks of these Examples 11-15 were also good inwriting performance.

From Table 4, the inks of Examples 16-19 containing glass flake pigmentsin 0.01-40% by weight relative to the total amount of the inkcompositions provided good writing performances and also providedhandwritings having a strong glittering feeling and spatial effect. Onthe other hand, the ink of Comparative Example 4 containing a glassflake pigment in less than 0.01% by weight relative to the total amountof the ink composition did not provide a strong glittering feeling andthe glittering feeling was poor and weak. Moreover, the ink ofComparative Example 4 also had a weak spatial effect which had beenreduced. On the other hand, the ink of Comparative Example 5 containinga glass flake pigment in more than 40% by weight relative to the totalamount of the ink composition had both strong glittering feeling andstrong spatial effect, but had poor writing characteristics.

From Table 5, the inks of Examples 20-23 containing metal coatedinorganic pigments as glittering pigments in 0.01-40% by weight relativeto the total amount of the ink compositions provided good writingperformances and also provided handwritings having strong glitteringfeeling. On the other hand, the ink of Comparative Example 6 containinga metal coated inorganic pigment in less than 0.01% by weight relativeto the total amount of the ink composition provided no strong glitteringfeeling and the glittering feeling was poor and weak. On the other hand,the ink of Comparative Example 7 containing a metal coated inorganicpigment in more than 40% by weight relative to the total amount of theink composition had a strong glittering feeling, but had poor writingperformance.

From Table 6, the inks of Examples 24-28 provided fluorescenthandwritings having a strong glittering feeling and spatial effect. Theinks of Examples 29 and 30 provided fluorescent golden handwritingshaving a strong glittering feeling. In the case of these inks, writingperformance was also good.

From Table 7, also the inks of Examples 31 to 34 wherein water-solubleresins including xanthan gum, polyacrylic acid and succinoglycan arecompounded provided handwritings having a strong glittering feeling andspatial effect. Moreover, from Table 8, in the case of the inks ofExamples 35-40 containing an aluminum powder pigment, titanium oxide andthe like, the colors of the handwritings were clearly shown up even on ablack paper because of their sufficient opacifying power, and glitteringhandwritings having a strong glittering feeling and spatial effect wereobtained.

From Tables 9 and 10, the aqueous glittering ink composition of Examples41-49 exhibited a glittering feeling suggestive of a jewel, aquamarine,and provided good fixability and good writing aptitude.

On the other hand, Comparative Example 8 provided a glittering feelingand spatial effect suggestive of a jewel, aquamarine, but no fixabilitywas obtained at all. In Comparative Example 9, a glittering feeling andspatial effect suggestive of a jewel, aquamarine, provided and writingaptitude was good, but no fixability was obtained at all. Moreover, inComparative Example 10, a glittering feeling and spatial effectsuggestive of a jewel, aquamarine, provided and fixability was good, butwriting performance was poor.

Furthermore, Table 10 shows that the ink compositions of the Examplespreferably contain the synthetic resin emulsions in 0.01-40% by weightin solids relative to the total amounts of the ink compositions. It alsoshows that the ink compositions of the Examples preferably contain theglass flake pigments in 0.01-40% by weight relative to the total amountsof the ink compositions.

Moreover, although each of the above-mentioned Examples applied the inkcompositions for those for ball-point pens, it can be used for otherwriting tools, printing inks, fields pertaining to coatings, tocosmetics, and the like.

Since the present invention is an aqueous glittering ink compositioncontaining a glass flake pigment, a water-soluble resin, a water-solubleorganic solvent and water, it can provide an unprecedented uniquehandwriting or coated film having a glittering feeling and spatialeffect stronger than that of aqueous ink composition using conventionalglittering pigments. In particular, in the case of the foregoing aqueousglittering ink composition containing a colorant together with a glassflake pigment, the strong glitter depending upon the hue of the colorantcan be provided to a handwriting or a coated film.

Furthermore, the aqueous glittering ink composition wherein a metalcoated inorganic pigment is compounded as a glittering pigment and whichcontains, at least, a water-soluble resin, a water-soluble organicsolvent and water can provide a handwriting or a coated film having astrong glittering feeling without loosing glittering feeling incomparison to the aqueous ink composition using conventional glitteringpigments. Moreover, in the case of the above-mentioned aqueousglittering ink composition containing a colorant together with a metalcoated inorganic pigment, the strong glitter depending upon the hue ofthe colorant can be provided to a handwriting or a coated film.

Moreover, the aqueous glittering ink composition containing a glassflake pigment, a water-soluble thickening resin, a water-soluble organicsolvent and water as essential ingredients and containing a bindercomponent, preferably a synthetic resin emulsion, for fixing the glassflake pigment to a handwriting or a coated film can improve fixabilityof the glass flake pigment to the handwriting or the coated film and cancontinue to provide a stronger glittering feeling and spatial effect tothe handwriting or the coated film without deteriorating inkcharacteristics or writing characteristics and without inhibitingeffects of the compounding of the glass flake pigment on the strongglittering feeling and spatial effect.

In addition, the present invention includes the identical subject matterdisclosed in the specification, claims of Japanese Patent applicationNo. 11-076868, No. 11-360187, No. 2000-002370, and No. 2000-002344 towhich is claimed priority for the present application.

What is claimed is:
 1. An aqueous glittering ink composition comprisinga metal coated inorganic pigment, a water-soluble resin, a water-solubleorganic solvent, and water, wherein said metal inorganic pigment is aninorganic pigment which is coated with metal which provides a metalreflecting surface.
 2. An aqueous glittering ink composition as setforth in claim 1, wherein the metal coated inorganic pigment iscontained in about 0.01-40% by weight relative to the total amount ofthe ink composition.
 3. An aqueous glittering ink composition as setforth in claim 1, wherein the metal coated inorganic pigment has mediandiameter of about 5-100 μm.
 4. An aqueous glittering ink composition asset forth in claim 1, wherein the water-soluble resin is contained inabout 0.01-40% by weight relative to the total amount of the inkcomposition.
 5. An aqueous glittering ink composition as set forth inclaim 1, further containing a colorant in about 0.05-15% by weightrelative to the total amount of the ink composition.
 6. An aqueousglittering ink composition as set forth in claim 1, further containingan opacifying pigment.
 7. An aqueous glittering ink compositioncomprising a metal coated inorganic pigment, a water-soluble resin, awater-soluble organic solvent, water, and a colorant, wherein said metalcoated inorganic pigment is an inorganic pigment which is coated withmetal which provides a metal reflecting surface.
 8. A writing toolhaving an ink container in which an aqueous glittering ink compositionis packed, wherein said aqueous glittering ink composition comprises ametal coated inorganic pigment which is an inorganic pigment which iscoated with metal which provides a metal reflective surface and having amedian diameter of about 5-100 μm, a water-soluble resin, awater-soluble organic solvent, and water.
 9. A writing tool as set forthin claim 8, wherein said inorganic pigment coated with a metal iscontained in about 0.01-40% by weight, relative to the total amount ofthe ink composition.
 10. A writing tool as set forth in claim 8, whereinthe viscosity of ink measured by an ELD viscometer 3° R14 cone; rotationspeed: 0.5 rpm; 20° C. is about 1000 to 10000 mPa·s.
 11. A writing toolas set forth in claim 8, wherein said aqueous glittering ink compositionfurther comprises a colorant in about 0.01-30% by weight relative to thetotal amount of the ink composition.
 12. A writing tool having an inkcontainer that is made of a hollow tube equipped with a ball-point pentip at one end, wherein said ink container has a aqueous glittering inkcomposition packed therein, said aqueous glittering ink compositioncomprising a metal coated inorganic pigment which is an inorganicpigment which is coated with metal which provides metal reflectingsurface and having a median diameter of about 5-100 μm and contained inabout 1.0-40% by weight, a water-soluble resin contained in about0.01-40% by weight and a water-soluble organic solvent contained inabout 1.00-40 % by weight relative to the total amount of the inkcomposition, and water.
 13. A writing tool as set forth in claim 12,wherein said water-soluble resin is a water-soluble thickening resin andthe viscosity of the aqueous glittering ink measured by an ELDviscometer 3° R14 cone; rotation speed: 0.5 rpm; 20° C. is about 1000 to10000 mPa·s.
 14. A writing tool as set forth in claim 13, wherein saidwater-soluble thickening resin is a microbial polysaccharide or aderivative thereof, selected from the group consisting of pollulan,xanthan gum, welan gum, rhamsan gum, succinoglucan and dextran.
 15. Awriting tool as set forth in claim 13, wherein said inorganic pigment iscoated with metal by means of metal deposition.
 16. A method for usingan aqueous glittering ink composition for a writing tool, the methodcomprising: providing an aqueous glittering ink composition whichcomprises a metal coated inorganic pigment which is an inorganic pigmentwhich is coated with metal which provides a metal reflecting surface andhaving a median diameter of about 5-100 μm, a water-soluble resin, awater-soluble organic solvent, and water.
 17. A method of claim 16,wherein the viscosity of said aqueous glittering ink measured by an ELDviscometer 3° R14 cone; rotation speed: 0.5 rpm; 20° C. is about 1000 to10000 mPa·s.
 18. A method for using an aqueous glittering inkcomposition for a writing tool, the method comprising: providing anaqueous glittering ink composition which comprises a metal coatedinorganic pigment which is an inorganic pigment which is coated withmetal which provides a metal reflecting surface and has a mediandiameter of about 5-100 μm, a water-soluble resin, a water-solubleorganic solvent, and water, packing said aqueous glittering inkcomposition into an ink container made of a hollow tube, and equipping aball-point pen tip with said ink container.
 19. A method of claim 18,wherein the viscosity of the aqueous glittering ink composition measuredby an ELD viscometer 3° R14 cone; rotation speed: 0.5 rpm; 20° C. isabout 1000 to 10000 mPa·s.
 20. A method for using an aqueous glitteringink composition for a writing tool, the method comprising: providing anaqueous glittering ink composition which comprises a metal coatedinorganic pigment which is an inorganic pigment which is coated withmetal which provides a metal reflecting surface and having a mediandiameter of about 5-100 μm and contained in about 1.0-40% by weight, awater-soluble resin contained in about 0.01-40% by weight, and awater-soluble organic solvent contained in about 1.00-40% by weightrelative to the total amount of the ink composition.
 21. A method ofclaim 20, wherein the viscosity of the aqueous glittering inkcomposition measured by an ELD viscometer 3° R14 cone; rotation speed:0.5 rpm; 20° C. is about 1000 to 10000 mPa·s.
 22. A method for using anaqueous glittering ink composition for a writing tool, the methodcomprising: providing an aqueous glittering ink composition whichcomprises a metal coated inorganic pigment which is an inorganic pigmentwhich is coated with metal which provides a metal reflecting surface andhaving a median diameter of about 5-100 μm and contained in about1.0-40% by weight, a water-soluble resin contained in about 0.01-40% byweight, and a water-soluble organic solvent contained in about 1.0-40%by weight relative to the total amount of the ink composition; packingsaid aqueous glittering ink composition into an ink container made of ahollow tube, an equipping a ball point pen tip with said ink container.23. An aqueous glittering ink composition comprising a metal coatedinorganic pigment, a colorant, a water-soluble resin, a water-solubleorganic solvent, and water, wherein said metal coated inorganic pigmentis an inorganic pigment coated not with a metal oxide but with a metal,and have a median diameter of about 5-100 μm and contained in about1.0-40% by weight relative to the total amount of the ink composition,said colorant in 0.01-30% by weight relative to the total amount of theink composition and said water-soluble resin is the water-solublethickening resin and the viscosity of aqueous glittering ink measured bya ELD viscometer 3° R14 cone; rotation speed: 0.5 rpm; 20° C. is 1000 to10000 mPa·s.
 24. An aqueous glittering ink composition as set forth inclaim 23, wherein the water-soluble resin is contained in 0.01-40% byweight relative to the total amount of the ink composition.
 25. Acomposition as claimed in claim 23, further containing an opacifyingpigment.
 26. A writing tool having an ink container in which an aqueousglittering ink composition is packed, wherein said aqueous glitteringink composition comprises an inorganic pigment coated not with a metaloxide but with a metal, having a median diameter of about 5-100 μm andcontained in about 1.0-40% by weight, a water-soluble resin is containedin 0.01-40% by weight, a colorant is contained in 0.01-30% by weight,relative to the total amount of the ink composition, an water, and saidwater-soluble resin is a water-soluble thickening resin and theviscosity of said aqueous glittering ink composition measured by an ELDviscometer 3° R14 cone; rotation speed: 0.5 rpm; 20° C. is 1000 to 10000mPa·s.
 27. A writing tool as set forth in claim 26, wherein saidwater-soluble thickening resin is microbial polysaccharides andderivatives thereof, selected from the group consisting of pollulan,xanthan gum, welan gum, rhamsan gum, succinoglucan and dextran.
 28. Awriting tool as set forth in claim 26, wherein said inorganic pigment iscoated with metal by means of metal deposition.
 29. A method for usingan aqueous glittering ink composition for a writing tool, the methodcomprising: providing an aqueous glittering ink composition whichcomprises a metal coated inorganic pigment, a colorant, a water-solubleresin, a water-soluble organic solvent and water, wherein said metalcoated inorganic pigment is an inorganic pigment coated not with a metaloxide but with a metal and have a median diameter of about 5-100 μm andcontained in about 1.0-40% by weight relative to the total amount of theink composition, said colorant in 0.01-30% by weight relative to thetotal amount of the ink compostion and said water-soluble resin is awater-soluble thickening resin and the viscosity of said aqueousglittering ink composition measured by an ELD viscometer 3° R14 cone;rotation speed: 0.5 rpm; 20 ° C. is 1000 to 10000 mPa·s.
 30. A methodfor using an aqueous glittering ink composition for a writing tool themethod comprising: providing an aqueous glittering ink composition whichcomprises an inorganic pigment coated not with a metal oxide but with ametal having a median diameter of about 5-100 μm, a water-soluble resin,a water-soluble organic solvent and water, packing said aqueousglittering ink composition into an ink container made of a hollow tube,and equipping a ball-point pen tip with said ink container.
 31. A methodof claim 30, wherein the viscosity of said aqueous glittering inkcomposition measured by an ELD viscometer 3° R14 cone; rotation speed:0.5 rpm; 20° C. is about 1000 to 10000 mPa·s.
 32. A method for using anaqueous glittering ink composition for a writing tool, the methodcomprising: providing an aqueous glittering ink composition whichcomprises an inorganic pigment coated not with a metal oxide but with ametal having a median diameter of about 5-100 μm and contained in about1.0-40% by weight, a water-soluble resin contained in 0.01-40% by weightand a water-soluble organic solvent contained in about 1.00-40% byweight relative to the total amount of the ink composition.
 33. A methodof claim 32, wherein the viscosity of aqueous glittering ink measured bya ELD visocmeter 3° R14 cone; rotation speed: 0.5 rpm; 20° C. is about1000 to 10000 mPa·s.
 34. A method for using an aqueous glittering inkcomposition for a writing tool, the method comprising: providing anaqueoue glittering ink composition which comprises an inorganic pigmentcoated not with a metal oxide but with a metal having a median diameterof about 5-100 μm and contained in about 1.0-40% by weight, awater-soluble resin contained in 0.01-40% by weight and a water-solubleorganic solvent contained in about 1.00-40% by weight relative to thetotal amount of the ink composition; packing said aqueous glittering inkcomposition into an ink container made of a hollow tube, and equipping aball-point pen tip with said ink container.